Fluorinated heterocyclic sulfides

ABSTRACT

Fluorinated-alkyl sulfides represented by [R f  (CH 2 ) n  S] z  Q where R f  is fluoroalkyl, n is 2 or 3, z is 1 or 2, and Q is an aryl, alkylaryl, alkyl heterocyclic or heterocyclic radical, are useful as surfactants or as intermediates for the preparation of salt-type, quaternary-salt, or amphoteric surfactants. 
     This application is a division of co-pending application Ser. No. 61,567 filed July 30, 1979, now U.S. Pat. No. 4,254,266, which is a division of Ser. No. 587,794 filed June 17, 1975, now U.S. Pat. No. 4,177,351 issued Dec. 4, 1979, which is a division of Ser. No. 396,649 filed Sept. 12, 1973, now U.S. Pat. No. 3,933,819 issued Jan. 20, 1976, which is a continuation-in-part of Ser. No. 171,325 filed Aug. 21, 1971, now abandoned.

This invention concerns novel fluorinated-alkyl sulfides containingaromatic and heterocyclic moieties. More particularly, this invention isdirected to fluorinated alkyl sulfides represented by [R_(f) (CH₂)_(n)S]_(z) Q where R_(f) is a radical selected from the group consisting ofperfluoroalkyl, perfluoroisoalkoxyalkyl and perfluoromonochloroalkylradicals having from 5 to 13 carbon atoms, preferably from 7 to 11carbon atoms, n is 2 or 3, z is 1 or 2, Q is an aryl, alkylaryl (i.e.,lower alkyl), alkylheterocyclic (i.e., lower alkyl, e.g., 1 to 4 carbonatoms), or heterocyclic group having up to 14 ring-carbon atoms. Aperfluoroalkyl radical is defined as one containing only carbon andfluorine; a perfluoroisoalkoxyalkyl radical contains only carbon,fluorine, and an oxygen in an ether linkage; a perfluoromonochloroalkylradical is one which contains only fluorine, chlorine and carbon; any ofthe foregoing radicals may be straight chain or branched chain. Thepreferred R_(f) radical is perfluoroalkyl. Representative R_(f) radicalsare, for example,

(CF₃)₂ CF(CF₂ CF₂)--

(CF₃)₂ CF(CF₂ CF₂)₃ --

C₇ F₁₅ --

C₁₁ F₂₃ --

(CF₃)₂ CFO(CF₂ CF₂)--

(CF₃)₂ CFO(CF₂ CF₂)₄ --

(CF₃) (CF₂ Cl)CF(CF₂ CF₂)--

C₇ ClF₁₄ --

C₈ F₁₇ --

CF₂ Cl(CF₂)₁₀ --

C₉ F₁₉ --

C₁₀ F₂₁ --

C₁₃ F₂₇ --

Q is an aryl, alkylaryl, or alkylheterocyclic, or heterocyclic group(i.e., heterocyclic means containing nitrogen, oxygen or sulfur atoms,or combinations thereof, in the organic ring). Such Q groups areexemplified by phenyl, naphthyl, pyridyl, pyrimidyl, thiazolyl,thiadiazolyl, oxazolyl, triazinyl, piperazinyl, piperidinyl,benzimidazolyl, benzothiozolyl, quinolinyl, furfuryl, thienyl and othersof this class. In addition, such aryl, alkylaryl, alkylheterocyclic, orheterocyclic groups can optionally contain substituents such as --Cl,--F, --NO₂, --CN, ##STR1## --OR, --NRR', ##STR2## --SO₂ NRR', --SR(where R and R' are independently hydrogen or lower alkyl).

In preparing the compounds of this invention, a fluoroalkylalkylenehalide is reacted with a mercaptan in the presence of a basic substance,such as NaOH, to produce the sulfide products according to the exemplaryreaction:

    z[R.sub.f (CH.sub.2).sub.n X]+Q(SH).sub.z +zNaOH→[R.sub.f (CH.sub.2).sub.n S].sub.z Q+zNaX+zH.sub.2 O

where n=2 or 3, z can vary from 1 to 2, X is Br or I, and R_(f) and Qare as defined earlier.

In the case of mercaptan reactants having a single --SH group (i.e.,z=1), the reaction may be more simply represented as:

    R.sub.f (CH.sub.2).sub.n X+QSH+NaOH→R.sub.f (CH.sub.2).sub.n SQ+NaX+H.sub.2 O

Representative mercaptan reactants are ##STR3##

Among the basic materials that may be used in the above-describedreaction are alkali metal hydroxides, e.g., KOH and LiOH, and preferablyNaOH, and such basic substances as triethylamine, sodium methoxide,potassium tert.-butoxide, and the like substances. The reaction iscarried out by bringing the above-described reactants together at atemperature within the range of about 50° to about 150° C., preferablyabout 80° to 100° C. The reaction is normally carried out underatmospheric pressure. Reaction periods ranging from 1 to 24 hours areusually adequate, with from about 2 to 6 hours normally satisfactory.

The reaction preferably is conducted with the reactants in admixture inmedium comprising organic polar liquid, which shows solvency for thefluoroalkylethylene halide, for example, methanol, ethanol, n-propanol,iso-propanol, n-amyl alcohol, n-hexanol, n-octanol, sec-butanol,n-butanol, isobutanol, tert-butanol, isoamyl alcohol, tert-amyl alcohol,2-pentanol, cyclohexanol, 2-ethyl-1-hexanol and mixtures of saidliquids. The weight ratio of polar solvent to fluoroalkylethylene halidewill generally be in the range of about 2:1 to about 10:1. In the morepreferred embodiments the solvent is essentially anhydrous.

The sulfides of this invention are selectively useful as surface tensiondepressants of organic and aqueous systems, and the acid-salt,quaternary-salt and amphoteric derivatives of the sulfides where Q is aheterocyclic nitrogen-containing moiety (e.g., pyridyl, piperidinyl,etc.) are especially superior surfactants due to their excellent abilityto lower surface tensions in aqueous systems. Amphoteric surfactants areprepared by reacting the appropriate sulfide with such reactants asmonochloroacetic acid, monobromoacetic acid, beta-propiolactone,propanesulfone, alkylene sulfites, and the like according to therepresentative reactions: ##STR4##

Quaternary salts are prepared by reacting the heterocyclicnitrogen-containing sulfide with a lower akyl halide quaternizing agent(R_(a) X, where R_(a) is lower alkyl and X is iodine, or less preferablybromine), for example, in a solvent such as diethyl ether or ethanol, orwith dimethyl sulfate. Acid salt derivatives are readily prepared fromthe nitrogen-containing sulfides by reaction with acids such as HCl, H₂SO₄, acetic acid and the like.

Compounds embodied herein may also be used to kill or inhibit the growthof bacterial microorganisms, including staphylococcus aureus andaspergillus niger.

In the following examples, which illustrate and clarify the presentinvention, the infrared spectrum of each synthesized product isconsistent with the structure set forth.

EXAMPLE 1 - Preparation of ##STR5##

A solution of 6.7 g (0.06 mole) of 4-mercaptopyridine and 2.4 g. (0.06mole) of NaOH in 35 ml. EtOH is heated for 10-15 minutes to 40°-50° C.The resulting brown mixture is cooled and then added slowly at ambienttemperature to a solution of 31.5 g. (0.06 mole) of (CF₃)₂ CF(CF₂)₄ CH₂CH₂ I in 100 ml. tert-amyl alcohol. The mixture is refluxed for 24hours, filtered to remove a very small amount of insoluble material, andthe filrate is stripped of solvent at 40°-50° C. to leave 65.0 g. oflight brown residue. This residue is in turn extracted with 5×100 ml.portions of hot ether and the ether extract washed with 100 ml. water,100 ml. 5% NaOH, and 100 ml. water, then dried and heated on a steambath to remove solvent. The brown liquid residue is distilled to afford23.8 g. (78% yield) of light brown liquid product b.p. 101° C. (0.08mm.) n_(D) ²⁵.2, 1.4127. Upon standing at room temperature, the product,##STR6## becomes crystalline, m.p. 34°-36° C.

Analysis. - Calcd. for C₁₄ H₈ F₁₅ NS: C, 33.15%; H, 1.59%; N, 2.76%.Found: C, 33.36%; H, 1.82%; N, 2.92%.

Preparation of Heterocyclic Amphoteric Surfactant

A mixture of 0.01 mole of the above-prepared product and 0.01 mole ofmonochloroacetic acid is heated slowly to 125°-130° C. with occasionalshaking in an oil bath, at which point the heat is turned off and thereaction mixture kept in the oil bath while the temperature slowly fallsto 30° C. There is obtained in 100% yield the amphoteric surfactant##STR7## a light brown solid, m.p. 178° C.

Analysis. - Calcd. for C₁₆ H₁₁ ClF₁₅ NO₂ S: C, 31.93%; H, 1.85%; Cl,5.89%; N, 2.33%. Found: C, 31.83%; H, 2.17%; Cl, 5.90%; N, 2.46%.

    ______________________________________                                        Surface Tension of Aqueous Solutions of the Heterocyclic                      Amphoteric Surfactant                                                         Concentration Dynes/cm @ 25° C.                                        ______________________________________                                        0.01%         18                                                              0.001%        32                                                              ______________________________________                                    

The unpredictable and exceptional performance of this heterocyclicamphoteric surfactant is even more impressive when it is compared tothat of the only commercially available fluorinated amphoteric, thealiphatic C₈ F₁₇ SO₂ NH(CH₂)₃ N⁺ (CH₃)₂ CH₂ CH₂ COO⁻, which has thefollowing surface activity

    ______________________________________                                        Concentration Dynes/cm @ 25° C.                                        ______________________________________                                        0.1%          19                                                              0.01%         27                                                              0.001%        40                                                              ______________________________________                                    

and which has a longer chain length in the expensive fluorocarbonportion.

The performance of the heterocyclic amphoteric also compares favorablywith the performance of the aliphatic surfactants disclosed in Hager andWalter's application, Ser. No. 145,556, filed May 20, 1971, and theinstant compounds advantageously do not contain hydrolyzable ester oramide linkages.

In addition, the heterocyclic surfactant inhibits the growth ofstaphylococcus aureus and aspergillus niger at a concentration of about500 ppm.

EXAMPLE 2 - Preparation of ##STR8##

Using the procedure of Example 1, o-mercaptobenzoic acid is reacted with(CF₃)₂ CF(CF₂)₄ CH₂ CH₂ I to produce, in 64% yield, the white solidproduct ##STR9## m.p. 114°-116°.

Analysis. - Calcd. for C₁₆ H₉ F₁₅ O₂ S: C, 34.93%; H, 1.65%; S, 5.83%.Found: C, 35.24%; H, 1.77%; S, 5.61%.

The compound inhibits the growth of staphylococcus aureus (ATCC 6438)when used at a concentration of 1000 ppm.

The surface tension of a 0.1% aqueous solution of the sodium salt of thecompound is 17 dynes/cm. at 25° C., again an unexpectedly exceptionalperformace when compared with that of a superficially similar aliphaticcompound (CF₃)₂ CF(CF₂)₄ CH₂ CH₂ SCH₂ CH₂ COONa (prepared via reactionof 3-mercaptopropionic acid with C₉ F₁₉ C₂ H₄ I in tert.-amyl alcohol)which produces a surface tension in 0.1% aqueous solution of 21dynes/cm. at 25° C.

Similar low surface tensions are obtained with other alkali metal saltsin accordance with the compound of this example, e.g., potassium,ammonium and substituted ammonium salts, i.e., anionic surfactantcompounds represented by the structure ##STR10## where M is alkalimetal, ammonium, or substituted ammonium.

EXAMPLE 3 - Preparation of ##STR11##

Following the procedure of Example 1, there is obtained a light greenoily liquid, ##STR12## which partially solidifies on long standing atroom temperature, b.p. 170° C. (2.8 mm.), n_(D) ²⁵.8, 1.4014.

Analysis. - Calcd. for C₁₆ H₆ Cl₂ F₁₉ NS: C, 28.42%; H, 0.90%; N, 3.87%.Found: C, 27.91%, H, 1.06%; N, 1.75%.

EXAMPLE 4 - Preparation of ##STR13##

A solution of 9.0 g. (0.06 mole) of 2-benzimidazolethiol and 2.4 g.(0.06 mole) of NaOH in 35 ml. abs. ethanol is heated for 15 minutes to40°-50° C. The resulting brown mixture is cooled and added slowly to awater-cooled solution of 31.5 g. (0.06 mole) of (CF₃)₂ CF(CF₂)₄ CH₂ CH₂I in 100 ml. tert-amyl alcohol. The mixture is refluxed for 19 hours,and worked-up as in Example 1. The crude product is recrystallized from50 ml. 80% ethanol to afford 23.2 g. (71% yield) of light brown solid,##STR14## m.p. 115°-119° C.

Analysis. - Calcd. for C₁₆ H₉ F₁₅ N₂ S: C, 35.18%; H, 1.66%; N, 5.13%.Found: C, 35.34%; H, 1.93%, N, 5.15%.

The compound inhibits growth of aspergillus niger at a concentration of1,000 ppm.

EXAMPLE 5 - Preparation of ##STR15##

Following the procedure of Example 4, a mixture of 0.06 mole of (CF₃)₂CF(CF₂)₄ CH₂ CH₂ I, 0.06 mole of 2-mercaptopyrimidine, and 0.06 mole ofNaOH in 40 ml. abs. ethanol and 100 ml. tert-amyl alcohol is refluxed toproduce a light green liquid product (84% yield), ##STR16## b.p. 128° (3mm.), n_(D) ²⁹.7, 1.4007.

Analysis: - Calcd. for C₁₃ H₇ F₁₅ N₂ S: C, 30.72%; H, 1.39%; N, 5.51%.Found: C, 30.82%; H, 1.72%; N, 5.10%.

The compound inhibits growth of aspergillus niger when used at aconcentration of 1000 ppm.

We claim:
 1. A fluorinated alkyl sulfide compound represented by theformula:

    [R.sub.f (CH.sub.2).sub.n --S].sub.z   Q

where R_(f) is selected from the group consisting of perfluoroalkyl,perfluoroisoalkoxyalkyl and perfluoromonochloroalkyl radicals havingfrom 5 to 13 carbon atoms, n is an integer of 2 or 3, z is 1 or 2, and Qis selected from the group consisting of the following: ##STR17##
 2. Thecompound of claim 1 wherein z is 2 and Q is ##STR18##
 3. The compound ofclaim 1 wherein Q is ##STR19##
 4. The compound of claim 1 wherein n is2.
 5. The compound of claim 4 wherein R_(f) is perfluoroalkyl havingfrom 7 to 1 carbon atoms.
 6. The compound of claim 5 wherein z is 2 Land Q is ##STR20##
 7. The compound of claim 5 wherein Q is ##STR21##